N-OCTADECYL 3,5-DI-t-BUTYL-4-HYDROXYBENZOATE

ABSTRACT

IN WHICH Y&#39;&#39; HAS A VALUE OF FROM SIX TO 20 INCLUSIVELY, ARE USEFUL IN THE STABILIZATION OF A VARIETY OF ORGANIC MATERIALS NORMALLY SUBJECT TO OXIDATIVE DETERIORATION. Organic polymeric substances such as polyolefins, lubricating oils, waxes and resins are among the organic materials stabilized.   Alkyl dialkylhydroxybenzoates of the formula:

United States Patent Dexter et a1. 1 1 Aug. 1, 1972 54] N-OCTADECYL3,5-DI-T-BUTYL-4- References Cited 72 I EI Z B lff M UNITED STATESPATENTS nventors: artin xter, riarci anor; 1 John Dem smack SpringValley; 3,112,338 11/1963 Smotney et a1. ..260/473 David HerbertSteinberg, Bronx, all i f Primary Exammer-Lorrame A. Wemberger AssistantExaminer-John F. Terapane [73] Asslgnee: Corporauon, New YorkAttorney-Karl F. Jorda, Martin J. Spellman, Jr. and

Bruce M. Collins [22] Filed:- Feb. 6, 1970 [21] Appl. No.: 7,417 [57]ABSTRACT Alkyl dialkylhydroxybenzoates of the formula: Related U.S.Application Data [60] Continuation of Set. N0. 616,794, Feb. 17, I

1967, abandoned, which is a division of Ser. (C 'II, H No. 354,434,March 24, 1964, Pat. No. I 3,330,859, which is a continuation-in-part of(lo\ver)alky1 Ser. No. 276,192, April 29, 1963, abandoned, which is acontinuation-in-part of Ser. No. in which y has a value of from six to20 inclusively, 164,618, Jan. 5, 1962, abandoned, whichis a are usefulin the stabilization of a variety of organic continuation-in-part ofSer. No. 148,738, Oct. materials normally subject to oxidativedeterioration. 1961, abandoned Organic polymeric substances such aspolyolefins,

lubricating oils, waxes and resins are among the or- [52] U.S. Cl...260/473 S, 44/70, 99/163, ganic materials stabilized.

252/407, 260/45.85, 260/398.5 51 Int. Cl ..C07c 69/78 1 Claim, NeDrawings [58] Field of Search ..260/473 N-OCTADECYL 3,5-Dl-T-BUTYL-4-HYDROXYBENZOATE CROSS REFERENCES TO RELATED APPLICATIONS Thisapplication is a continuation of Ser. No. 616,794 filed Feb. 17, 1967,how abandoned which in turn is a division of copending application, Ser.No. 354,434, filed Mar. 24, 1964 now U.S. Pat. No. 3,330,859, which is aconfinuation-in-part of Ser. No. 276,192, filed Apr. 29, 1963 nowabandoned, which is a continuation-in-part of Ser. No. 164,618, filedJan. 5, 1962 now abandoned, which is a continuation-in-part of Ser. No.148,738 filed Oct. 30, 1961, now abandoned.

THE INVENTION This invention pertains to novel carboxylic acid esterswhich are useful in the stabilization of organic materials normallysubject to oxidative deterioration.

Materials which are stabilized according to the present inventioninclude synthetic organic polymeric substances such as vinyl resinsformed from the polymerization of vinyl halides or from thecopolymerizan'on of vinyl halides with unsaturated polymerizablecompounds, e.g., vinyl esters, -a,B-unsaturated acids, a,B-unsaturatedesters, a,B-unsaturated ketones, a,B-unsaturated aldehydes andunsaturated hydrocarbons such as butadienes and styrene; poly-a-olefinssuch as polyethylene, polypropylene, polybutylene, polyisoprene and thelike, including copolymers of poly-a-olefins; polyurethanes such as areprepared from polyols and organic polyisocyanates; polyarnides such aspolyhexamethylene adipamide; polyesters such as polymethyleneterephthalates; polycarbonates; polyacetols; polystyrene,polyethyleneoxide; and copolymers such as those of high impactpolystyrene containing copolymers of butadiene and styrene and thoseformed by the copolymerization of acrylonitrile, butadiene and/orstyrene. Other materials stabilized according to the present inventionincludes lubricating oil of the aliphatic ester type, e.g.,di-(2-ethylhexyl)-azelate-, pentaerythitol tetracaproate and the like;animal and vegetable derived oils, e.g., linseed oil, fat, tallow, lard,peanut oil, cod liver oil, castor oil, palm oil, corn oil, cotton seedoil and the like; hydrocarbon material such as gasoline, both naturaland synthetic, diesel oil, mineral oil, fuel oil, drying oil, cuttingfluids, waxes, resins and the like, fatty acids such as soaps and thelike.

In general the stabilizers of this invention are employed from about0.005 percent to about percent by weight of the stabilized composition.A particularly advantageous range for polyolefins such as polypropyleneis from about 0. 1 percent to about l per cent.

The compounds of the present invention are llowi-nulkgl 1 wherein y hasa value of from 6 to 30 inclusively.

Particularly useful compounds of the above class are those of theformula:

(Ullshfl in which y has a value of from 6 to 20.

By the term alkyl and derivations thereof such as alkylene or alkanoyl"is intended when used herein a group containing a branched or straightchain hydrocarbon chain of from one to 20 carbon atoms inclusively.Representative of such alkyl groups are thus methyl, ethyl propyl,butyl, t-butyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, eicosyland the like.

When the term alkyl is herein qualified by the designation (lower),there is intended a branched or straight chain hydrocarbon of from oneto about six carbon atoms.

It will be observed, that the di(lower)alkylphenolic moiety in FORMULA lexhibits at least one (lower)alkyl group in a position ortho to thehydroxy group. The other (lower)alkyl group is either (a) in the otherposition ortho to the hydroxy group or (b.) meta to the hydroxy groupand para to the first (lower) -alkyl group. Although not so limited,these (lower)-alkyl groups are preferably branched groups such ast-butyl. Other arrangements, such as for example a 3-t-butyl-6-methyl-p-phenolic moiety, are however clearly envisioned.

The compounds of the present invention may be prepared via usualesterification procedures from a suitable alcohol and a benzoic acid ofthe formula:

1 (lower) all: yl

or an acid halide, acid anhydride or mixed anhydride thereof. g

Similarly the novel esters of this invention may be prepared byconventional methods of transesterification.

The compounds of this invention may also be prepared -by treating adialkylphenol with a halo-ester of the formula:

Z -()-(O lI2y)ll in which Z is halogen; e.g., Cl, Br, etc.

Stabilized compositions embracing the compounds of this invention, aloneor in combination with other stabilizing materials, are more fullydescribed in U.S. Pat. No. 3,285,855 issued Nov. 15, 1966 which wasfiled as a continuation-in-part of our then copending application Ser.No. 164,618 filed Jan. 5, 1962, now abandoned.

The following examples, presented for illustration and not limitation,will further serve to typify the nature of the present invention. Inthese examples, parts are by weight unless otherwise specified andtemperature is expressed in degrees Centigrade. The relationship betweenparts by weight and parts by volume is as that of grams to cubiccentimeters.

EXAMPLE 1 n-Octadecyl 3,5-di-t-butyl-4-hydroxybenzoate a. Methyl3,5-di-t-butyl-4-hydroxybenzoate 40 parts of 2,6-di-t-butylphenol aredissolved in 150 parts by volume of methanol. To this solution are added60 parts of sodium hydroxide as a 40 percent aqueous solution, followedby 1 part of cupric sulfate. The resulting mixture is then treated with40 parts of carbon tetrachloride, which is added dropwise over a -20minute interval. This causes the reaction temperature to rise to 7580.Stirring is continued for 10 minutes after the addition of allreactants.

After cooling to room temperature, the reaction mixture is poured into700 parts of water and the resulting solids are filtered to yield 68.5parts of product. Further purification is achieved by recrystallizationfrom aqueous acetic acid, benzene-hexane or, cyclohexane. Use of thelast named solvent gives almost white crystals, m.p. l62l 63.

b. n-Octadecyl 3,5-di-t-butyl-4-hydroxybenzoate Methyl3,S-di-t-butyl-4-hydroxybenzoate (6.6 parts), 13.5 parts of n-octadecylalcohol and 0.2 parts of sodium methylate are mixed at room temperatureand then heated at l50+ for 10 hours. During the final 2 hours ofheating, an initial vacuum of 10-33 mm is applied, followed by a highvacuum of 0.5-1 mm for 0.2 hours. Removal of most of the impurities isaccomplished by distillation at l25185/0.25 mm. The residue (11.0 parts)is further purified by crystallization from acetone-cyclohexane to givea white crystalline product, melting at 65-67.

EXAMPLE 2 n-Hexyl 3,5-di- -butyl-4-hydroxybenzoate n-Hexanol (1.84parts) and 1.82 parts of triethylamine are dissolved in 50 parts byvolume of dry benzene. 3,5-Di-t-butyl-4-hydroxybenzoylchloride (4.72parts) dissolved in 25 parts by volume of dry benzene is added dropwisewith stirring at 2530-" over a period of 10 minutes. The reactants arethen heated under reflux for 3 hours after which time 1.6 parts oftriethylamine hydrochloride are removed by filtration. The yellowfiltrate is washed with saturated sodium chloride solution, twice with2N aqueous sodium carbonate solution and then again with saturatedsodium chloride solution. After drying the solution over anhydroussodium sulfate, the solvent is removed by evaporation. Six parts of asolid residue are thus obtained and purified by vacuum distillation. Then-hexyl 3,5-di-t-butyl-4-hydroxybenzoate distills at l50-l55 /0.l mm,m.p. -72. The yield of the pure product 18 1 etracosyl3,5-di-t-butyl-4-hydroxybenzoate is prepared in an analogous manner withtetracosyl aicohol.

EXAMPLE 3 n-Dodecyl 3,5-di-t-butyl-4-hydroxybenzoate n-Dodecanol (2.78parts) and 1.88 parts of triethylamine are dissolved in 5 0 parts byvolume of dry benzene and 5.0 parts of3,5-di-t-butyl-4-hydroxybenzoylchloride dissolved in 25 parts by volumeof dry benzene are added dropwise with stirring at 25-30 over a periodof 10 minutes. The reactants are then heated under reflux for 3 hours.Triethylamine hydrochloride (1.85 parts) is removed by filtration andthe yellow filtrate is washed with saturated sodium chloride solution,twice with 2N aqueous sodium bicarbonate solution, and again withsaturated sodium chloride solution. The solution is then dried overanhydrous sodium sulfate and the solvent evaporated under vacuum. Theresidue comprising n-dodecyl 3,5- di-t-butyl-4-hydroxybenzoate (8 parts)is distilled at l89l 93/ l-2 microns, m.p. 4753.

What is claimed is:

1. The compound n-octadecyl 3,5-dit-butyl-4- hydroxy benzoate.

